Organic mercury compounds



United States Patent 3,189,631 ORGANIC MERCURY COM POUNDS Herbert C. Stecker, 1 Bridle Vay, Ho-Ho-Kus, NJ. No Drawing. Filed Oct. 29, 1962, Ser. No. 233,861 3 Claims. (Cl. 260431) This application is a continuation-in-part of my 00- pending application Serial No. 759,845, filed September 9, 1958, now U.S.,Patent 3,076,832.

This invention deals with new organic compounds of mercury, useful as fungicides and bactericides for nontherapeutic purposes in the preservation of materials other than foods, and the like. These novel compounds have at least one ether type of bridge linkage, the linkage being effected through a polar element (such as O, P, As, S, N,Sb, etc.) which, although bare of organic radicals, has carried at least two active hydrogen atoms prior to the reaction set forth herein.

The novel compounds of the present invention are produced by reaction of .three ingredients, namely, (1) an aliphatic substituted unsaturated hydrocarbon carrying at least one labile negative substituent, (2) an anion-carrying divalent mercury compound, and (3) an organic radical-free compound having at least two active-hydrogen atoms attached to a polar atom selected from the right hand series of Groups V and VI of the periodic table.

This latter organic radical-free compound hereinafter shall be referred to as a bare compound, i.e., one bare of organic radicals.

According to the present invention, allyl chloride, for example, may be reacted with mercuric oxide in the presence of acetic acid and Water (bare active-hydrogen-carrying compound) to produce chloropropyl mercuric acetate ether in accordance with the following reaction:

2C1CH CH:CH E 2Hg(0 0 0 CH ClGH -[CH-JJH -HgOOOGH;

O 2CHaC O OH ClCH -lH-CH HgOOOCH In this case, the labile hydrogens leave the water molecule presumably to form free acetic acid, and the remaining oxygen joins onto the two allyl chloride molecules to form an ether bridge linkage. I Likewise, methallylthiocyanate, mercuric oxide, trichloroacetic acid, and phosphine can combine according to the following reaction:

From the foregoing, it is apparent that the first ingredient of the reaction mixture employed for this invention is an aliphatic unsaturated hydrocarbon containing a labile substituent group, such as a halogen. Bernthsen, in his Textbook of Organic Chemistry, Sudborough edition, D. Van Nostrand Co., 127, page 58, states that halogen substituents, such as chlorine, bromine, iodine and fluorine, are labile or readily-replaceable groups. Other such labile groups found suitable for the purpose of the present invention are SON, CNS, OCN and CNO groups. Although only one such group must be present, more than one, and up to twenty of such groups may be present. This labile group is necessary for the reaction to proceed substantially to completion in presence of acid, although the group itself does not necessarily undergo any apparent reaction during the formation'of the compounds of the present invention. The aforesaid hydrocarbon reacting compound for the reaction may contain other substituents, such as ether linkages, and the like, which do not enter into the reaction involved herein, provided such latter groups do not interfere with the aforesaid desired reaction by steric hindrance, excessive weakening of the unsaturated bond, or otherwise. Hydrocarbon compounds of this type found suitable for this purpose in the reaction set forth herein include allyl chloride, methallyl chloride, propargyl bromide, 2-chloroethylvinyl ether, vinylidene iodide, vinyl bromide, oleyl fluoride, perchlorododecyl vinyl ether, oleyl iodide, allyl \thiocyanate, allyl isothiocyanate, methallyl isothiocyanate and the like. It is preferred that such unsaturated hydrocarbons have 2 to 30 carbon atoms per molecule, although the most desirable ones at the present time have 2 to 10 carbon atoms per molecule. These latter hydrocarbon compounds may be straight chain or branched, provided the unsaturation is in reactive form.

The second ingredient in the reaction mixture is a divalent mercury compound carrying an anion, such as mercuric acetate, mercuric stearate, mercuric bromide, mercuric chloride, mercuric hydroxyacetate, mercuric phosphate, mercuric propionate, mercuric nonoate, mercuric sulfate, mercuric borate, mercuric malonate, mercuric trichloroacetate, mercuric terephthalate, mercuric hydroxyacetate, and the like. It is preferable first to start with a low molecular weight organic acid such as acetic, and then, if an inorganic salt or salt of a sluggishly acting organic acid (such as nonoic) is desired, the latter acid is added later, whena salt exchange occurs. These mercury compounds may be formed in situ during the reaction, by use of mercuric oxide (HgO) using the appropriate anionforming acid, such as acetic, propionic, hydroxyacetic, and like acid, it being understood that the acid employed would not make'the mercury unreactive or too slowly reactive for the purpose of the present invention. The in situ formation of the mercury compound often is more preferable, as it aids in controlling the extent of'the reaction, as will be explained hereinafter.

The third ingredient in the reaction mixture is a bare active-hydrogen compound, i.e., an active hydrogen compound which is free of organic radicals on the activehydrogen-carrying polar element. Such active-hydrogen compounds may be water, hydrogen sulfide, arsine, ammonia, phosphine, hydrogen selenide, stibine, and other bare compounds of the right hand elements of Groups V and VI of the Periodic Table, carrying at least two active hydrogens, and thus capable of forming an ether type bridge in the reaction product. For example, such polar elements in Group V would be N, P, As, Sb, etc., while those in Group VI would be 0, S, Se, Te, etc. Elements having atomic numbers of not over 52 are most desirable.

According to the present invention, allyl chloride, phosphine and mercuric trichloroacetate react in the follow- The bridging of the phosphorus plus its unreacted hydrogen atom takes place at the dangling valence indicated, While the reacted active hydrogens of the phosphine enter into Water formation. This reaction may be written empirically, as follows:

wherein R represents an unsaturated hydrocarbon compound containing the labile substituents X E represents the bare element carrying the reacting active hydrogen atoms (H and the non-reacting activehydrogen atoms (H' Hg represents an atom of divalent mercury, b represents the reacting valence (or number of active. by

.follows:

drogen's) of the bare element and thus is equivalent to the number of mercury atoms reacting, A represents the 7 i V anion salt portionattached to the bivalent mercuryatom, represents the number of mercury anions reacting, and mirepresents the number of Es reacting. For example, j

if RX is perchlorododecyl vinyl ether, then m hasa I value'j of 20. R,'Wl1lCh represents a hydrocarbon group Qc'ar'rying labile su'bstituent X, has 2 to 30 carbon atoms. I

The number of substituents d can vary from 1 to 20. V For example, if allyltrichloride was reacted with two ofthe active hydrogenratoms of phosphine, and with mercury phosphate, the following .reaction would take place: V J a Since the bridging of the PH takesplace'at thedangling valence, the reaction product can have the structure as .C13C.CH..OHZH

7 PH 7 Po;-n .o132.cn.ocn ClsCl lBLCH lilg f int i i Hg.CHz.Ei.CCla

' onocuomH -Poi 7 in: oiaocncmn Inthe event methallyl chloride was reacted with all three of the active hydrogen atoms of 'arsine, and with mercury phosphate, the following reaction would take place:

scrocmon, HSAs 3Hg0 Hal 0,

And the reaction product can have the structural formula as follows:

ore-0H3 As-CH 1 Por Hz-HE Thesenovel compounds may be produced simply by I mixing the specified substituted unsaturated hydrocarbon compound with thespecified mercuric salt or with mercuric oxide and an acid corresponding to the salt, with j the precautions already mentioned, in the presence of the desired bare active hydrogen compound. .The acid also may be employed in excess as the reaction solvent; Ac-. cording to the general procedure, mercuric oxide is dis- .tswicncuomngnroi+sn to produce a better yield.

In the case of compounds wherein allot the active hydrogens are reacted, such as those illustrated by Example 1 of Table I, it is considered necessary to add more than the theoretically required quantity of There is usually a liberation of-heat duringthe stirring 7 operation, after'which the product may-be recovered by precipitation, evaporation of the solvent, or. by drying from the frozen state. The ,productsformed vary from highly volatile to relatively non-volatileliquids and crys-: talline or amorphous solids. When using'frnercuric ch10 ride and other mercury salts which tendto. react slowly.

water in order 1 or incompletely, reaction maybe carried out as specially {'11 outlined above, V V 1 As stated previously,'-.although "R has been specified as a specially substiu'ted hydrocarbon group, it isifto be understood that this group may contain one or more substituents which do not "enter into the reaction ofthe' present invention and which do not interfere with said reaction by'steric hindrance excessive weakeningofthe saturatedhydrocarbon, .or otherwise, Such other substituentsf may include'halog'ens, ether-linked groups, nitro groups, as well as other known group s. W I; Although the mercury salt, as such, may beaddedslow ly to the other reactants in the solvent to prepare-the products of the present invention, it has been found that control of the reaction is more easily obtained'by addition of mercuric oxide to the otherreactants, including the acid reactable with the'oxide, and the solvent, as outlined in Example l of Table I, with the precautions,already mentioned, being observed. a a

a Biological tests on compounds made in accordance with the present invention have shown that their activity-, in

relation to phenyl mercury acetate (the present standard of organo-mercury compounds), is, on the average, over 23% greater, i.e., theyrequire 23% less mercury metal by wei ht in the'treating compositions to produce the same biocidal effect, while fact results in; a decidedly unsaturated bond of the reacting parent substituted un favorable economic advantage inview' of the high cost of mercury. Although the reason for thisis not entirely established, it is believed that the highbiocidal activity of the compounds of the present inventionvis attributablein part, at least, to the presence in the molecule a of a labile activating atom ,(e.g., a halogen atom) together with a lipoph yllic group (e.g., an ether linkage) 7 which, with other concommitant portions of the molecule,

enable more 'eifective penetration of the mercury atom through the cell wall ofthe mircoorganismh 4 Among other advantages of the compoundsof the present invention are simplicity of manufacturqemployment solved in acetic acid and the water, for example, or the hydride of the polar elementtphosphine, arsine, hydrogen sulfide, hydrogen selenide, ammonia, or stibine).isbubbled through or otherwise added, as in solution form dissolved in acetic acid solvent (to prevent reduction ofthe mercury compound), with further acetic acid in the molar, amount required for production of the particular product, as

indicated in Table I. The reaction preferably is done at low temperature, say just above the melting point of the acetic acid. The unsaturated hydrocarbon containing a labilesubstituent (e.g., allyl chloride) is then added to the reaction mixture, using an excess of acetic acid as the 0 reaction medium. It will be noted in Examples 13-17 of TableI, that the reaction first is carried out with acetic 1 acid, after which the slow-reacting'acid is added, where-,

upon a salt interchange occurs. Reaction is conducted at low temperature, after which the mixture is heated to C. and filtered. The product separates on cooling the filtrate, but further separation may be accomplishedby dilution of the filtrate with water.

of less equipment, and high yields resulting in'lower material costs. Furthermore, molecular structures may be synthesized having characteristics specifically, desired for J the biocidal problem encounteredf The examples given herein and in Table I present a series of compounds preparedi in accordance with, the present invention. Their biocidal activity is' given as' 60' the precentage of that obtained with PMA (phenylmercuric acetate); This comparative biological activity was determined byuse of Difcojnutrient agar, inoculated with Staphylococcus aureus and poured into Petri dish plates. Zones of inhibitionwere determined in triplicate V for each product after [24-hour incubation period at deduced. For example, if PMA at 1000 ppm. produced. 7

a zone inhibition measuring 24 mm., and it was found that the same zone size was obtainable with the new compound at 500 p.p.m., then this new product would be considered to be 100% more efiective than PMA.

This invention may be more readily understood by reference to the following examples which depict many sulfidewere reacted in excess acetic acid solvent, at about the melting point of acetic acid, as in Example 1. When the reaction was completed, the product was re covered, acetic acid was again added and the mixture phases of the present invention: 5 was allowed to warm up to room temperature and stand EXAMPLE 1 over night. The separated compound was found to have V a molecular weight of 704. The compound had an em- Two moles of allyl chlor de, about 10 moles of water, i i l f l f C H O Hg SC1 and wa found to be two moles of mercuric oxide and two moles of acetlc the following compound: acid Were reacted by adding the mercuric oxide slowly 10 C C with stirring to the mixture of other compounds in exlcHilH'cfiz'flgooccHa cess acetic acid as solvent. After 30 minutes (when all s mercuric oxide was consumed), the reaction mass was CwmECmHgOOCcH warmed and stirred until no morgamc mercury ions EXAMPLE 3 were detectable by the addition of a small test portion to dilute NaOH solution. The resulting product was Into a mixture of two moles of methyallylthiocyanate, found to have the empirical formula C I-I O Hg C1 two moles of mercuric oxide, and three moles of trichloroand was obtained in quantitative yield after stripping otf acetic acid, phosphine dissolved in acetic acid was added of the solvent. It was identified as: while stirring at low temperature until one mole of the C1 CH2 CH CH2 Hg0OCCH3 20 phosphine was reacted. The compound, recovered as I in Example 1, had an empirical formula of o1o Hr-bn-o H -HgO o 0 CH; 14 15 4 z z 2 6 The determined molecule weight of the compound oband a molecular weight of 984. It was identified as: tained was 688. The calculated amount of mercury was NCS CH ()H QH HgOOQCC1 58.3%. Actually, 58.2% was found. Its biological ac- 5 PH tivity over that of phenyl mercury acetate (PMA) was 3 J) 53 3% NCSCH HOH .HgOOCCCl3 EXAMPLE 2 H3 Two moles of allyl chloride, two moles of acetic acid, The compound had a biological activity of 46.7% over two moles of mercuric oxide and one mole of hydrogen that of PMA, based on the mercury content.

Table I Percent Hg Biological activity Percent ac- Reactmg components Compound formed General formula MW 0211- Ratio to tivity over cu- Found corresp. that of lated phenyl PMA,

Hg salt basis Hg content 1. Allyl chloride Cl-GHz-OHCHzHgOOOOHa CmHmOsHgzClz 688 58.3 58.2 2.09 53.3

Mercuric oxide Acetic acid 0 Water ClCHz-OHCHzHgOOCCH 2. Methallylthiocyanate CH3 C iH O HggS PNzCla 984 40.8 40.7 1. 29 33.1

lVIercuric oxide Trichloracetic acid NCSCHOHCHZHgO 0 c 0 C13 Phosphiue mole) 1' 1: NCS(I3HGHCH Hg0 o 0 0 C13 a. Allyl chloride Cl-OHzCH-CHzHgOOOCE C15H2AO6H3PC13 1,040 57.8 57.5 1.28 23.3

Mercuric oxide Acetic acid P-CHCHzHgO O 0 CH3 Phosphine (A mole) V (EH2 C1CHzCH 01 Hg-OOCOHa 4. Allyl chloride Cl-GH CH-CHzHgOOCCHa C10H1704HE2ASC12 748 53.6 53.4 1.26 20.5

Mercin'ic oxide 1 Acetic acid ASH Arsine mole) I ClCH2CHCHgHgO o 0 CH 5. Allyl chloride ClCHzCHCH2HgOOCCHa CJ5H24O5H3ASC13 1,084 55.6 55.5 1.28 24.1

Mercurie oxide Acetic acid As-CH-OHgHgO 0 0 CH3 Arsine (A mole) C1CH2(]JH 0H2 (3H2 01 Hg-OOCCH 6. Allyl chloride ClCHzCHCHzHgOOOOH CwHmOiHgzOh 704 57.0 56.8 1.67 12.1

Mercuric made I Acetic acid S Hydrogen sulfide l Cl-CHzOHCH2HgOOOCHz I V Tcible 1Coniiii1icd Percent Hg 7 3 Biological activity 7 4 7 V V V .Peiqcent ac Reacting components: Compound formed General formula MW Oal- Rat o to tivity over 7 7 cu- Found corresp. that of lated' plienyl PMA'; 'Hg salt basis Hg content 7. Methallyl chloride CH3 V CjZHzQOiHQzSfiCl: 779 5 2.8 52.4 1.28 2.5;0

Mercuric oxide I F a Acetic acid ClCHCH-GH2HO O 0 CH Y Hydrogen selenide r G1'(I3H CH'CHzHgO 0 c CH3 0113, V 5 j s; Allyl chloride ci-cHz0H-cH2Hgo o 0 CH cmianolH gNciz as? V 53. 4 7 5s. 5 '2. 05 52.5 Mercuric oxide 7 V i" Acetic acid N H V Ammonium acetate l l mo C1.OHTOH.CH2HgOOCCH3 V V V 7 9. Allyl chloride ClCH -CHCHzHgO O C CH3 CiaHziosHgaNCls 1 ,023 58. 8 58. 6 l. 28 22. 5

Mercmic oxide V Acetic acid V NCHCH2HgO O 0 CH Ammonium acetate I mole) V 7 CH 'C1OH2(|JH CI (3H2 7 Hg-O O C CH3 7 i0. Allyl chloride OlCH -CHCHqHgO 0 0 CH: owHnoiH zsbcii 795 50. 4 49. 8 0. 96 6. Mercuric oxide i Acetic acid SbH Stibine mole) I r V C1-CH2CHCH2HO O 0 CH 11. Ally] chloride Cl-CH CHCH2HgO O C CH3 C15H2iOsHg3SbC13 1 ,131 53. 2 53. 0 1. 26 23. 3 Metcuric oxide V Acetic acid Sb-CHC-H;Hg0 O 0 CH j Stibine mole) r l q C1GH2(}3H $152 (3H2 Cl V HgO 0 0 CH3 a 12. Allyl isothiocyanate SONOH2-CHCH2.HgO O C GH OH cizHisorHgzszNz .765 52. 4 52. 6 1. 65 45. 3 Mercuric oxide l V Hydrcxyacetic acid 0 Water I 7 s0 101 2cHT-0H2.Hg0o c CHzOH Vinyl bromide 0 C H6O Hg2l3r2 731 5 4. 9 l 5415 2. 01 55. 0 Mercuric oxide a Malonic acid BrC H-CH.HgOC Acetic acid r \Vatei (I) /CH2 BrCH-OH.HgOC

14. Oleyliodide O CasHTsOoHgzPzIz l ,357 29. 6 29. 1 1. 14 25. 2 Mercuric oxide 7 I! Phosphoric acid 1(OH3) OHCH.HgOP-OH (ethyl ester) Acetic acid 0 C2H Water O 2)1 i I(CH2)sCHCH.Hg OI" (CH2) 7 O C 2H5 V W 15. Z-flugroethylvinyl 0-02H4F ozlHaowngzasFzNan 1,031 .38. 9 39.0 1. 20 25. 5

1 et er 1 Mercuric acetate CH-CHz.HgO O C C O ONa Sodium terephthalate (hemi salt) ASH Acetic acid l Arsine (1713 01123150 0 O O O ONa 7 OC2 4F V 16. Vinylidene chloride Cl2-0CHz.HgO O C(CH2)7CH3 CzzHaoo HgzAsClgflu 985 V 40. 7 40. 3 1. 15 19. 2 Mercuric oxide l V Nonoic acid ASH Acetic acid Stibine Clz-CCH2.HgO O 0 (011919113 1' Vinyl chloride Cl CHCH2.HgH BO C;H1DO7Hg2B2C12 664 60. 4 60. 3 2. 03 50. 2

ercun'c oxide 7 I Boric acid 0 i Acetic acid 7 Water ClCH-CH2.HgHzBO I claim:

1. An ether type bridge linkage-containing organic compound reaction product of a mercuric anionic salt, a bare active-hydrogen-carrying compound having at least two active hydrogen atoms, and an aliphatic mono olefine carrying at least one labile substituent group, said reaction product having the formula:

m( n)m( d )b c wherein:

R represents a saturated hydrocarbon group carrying 2 to 30 carbon atoms,

X reprewnts a labile substituent on R, selected from the radicals consisting of halogen, SCN, CNS, OCN and CNO,

E represents a bare element serving as a bridge and selected from the class consisting of right hand elements of Groups V and VI of the Periodic Table, other than oxygen,

H represents an unreacted active hydrogen atom remaining on E,

Hg represents an atom of divalent mercury,

A represents an anion salt portion attached to the mercury atom,

11 represents the number of mercury atoms, and is a numeral from 2 to 6,

0 represents the number of anions A, and is a numeral from '1 to 3,

10 OlCH CHOH .HgOOCCH o1oH1oHoH2-H 0 0 0 CH 3. An ether type bridge linkage-containin g organic compound reaction product having the formula:

O1CHzCH-OH .HgO 0 0 CH3 NH o1oH2-orroH,.H 0 o 0 CH3 References Cited by the Examiner Berichte der Deutschen Chemischem Gesellschaft, 33 (1900), pages 13401364 (pages 1340-42 and 1350-53 25 relied on).

TOBIAS E. LEVOW, Primary Examiner. 

1. AN ETHER TYPE BRIDGE LINKAGE-CONTAINING ORGANIC COMPOUND REACTION PRODUCT OF A MERCURIC ANIONIC SALT, A BARE ACTIVE-HYDROGEN-CARYING COMPOUND HAVING AT LEAST TWO ACTIVE HYDROGEN ATOMS, AND AN ALIPHATIC MONO OLEFINE CARRYING AT LEAST ONE LABILE SUBSTITUENT GROUP, SAID REACTION PRODUCT HAVING THE FORMULA: 